DE60023171T2 - ENZYMATIC MODIFICATION OF THE SURFACE OF A POLYESTER FIBER OR A PART OF POLYESTERS - Google Patents

Abstract

A method is provided for improving the uptake of a cationic compound onto a polyester article starting material, comprising the steps of: (a) obtaining a polyesterase enzyme; (b) contacting said polyesterase enzyme with said polyester article starting material under conditions and for a time suitable for said polyesterase to produce surface modification of said polyester article starting material and produce a surface modified polyester; (c) contacting said modified polyester article, subsequently or simultaneously with said step (b) with a cationic compound whereby adherence of said cationic compound to said modified polyester is increased compared to said polyester starting material. Also disclosed is a method for increasing the hydrophilicity of a polyester to improve fabric characteristics such as stain resistance, wettability and/or dyeability.

Description

The The present invention relates to the field of modification of synthetic Fibers used in the manufacture of for the production of textile fabrics, Textiles, carpets and other consumer items Yarns are used. In particular, the present invention relates the enzymatic modification of the characteristics of a polyester fiber, so that such polyester for Post-modification treatments are more susceptible.

B. State of the art

polyester are manufactured synthetic compositions, which either long-chain synthetic polymer comprising at least 85% by weight of an ester of a substituted aromatic carboxylic acid, inclusive, but not limited on, substituted terephthalic acid units and para-substituted hydroxybenzoate units. Of the Polyester can be fiber, yarn, fabric, foil, resin or powder to have. Numerous chemical derivatives have been developed, for Example, polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT) and polyethylene naphthalate (PEN). However, PET is the most common manufactured linear polymer and represents the majority of those in the industry Polyester used today.

thermoplastic Polyester can selectively in each of the processing steps of the polymerization and fiber formation are technically produced. This flexibility and the Range of properties allows the production of a wide range of products made of polyester for markets such as the clothing, home furnishings, upholstery, foil, Hard and soft container, Nonwoven textile, tire and carpet industries. As a result of these, polyester became the predominant reinforcing fiber in the United States States. About that out while over the Over the past 30 years, cotton has been steadily growing slowly and steadily of the volume consumed and wool practically consistent polyester, began to gain in importance. Also reached Polyester a high degree of Consumer acceptance due to its strength and increasing quality and variety of textile fabrics made using such fibers can be produced. Other polyester markets, like fibrous filler and nonwoven articles, are constantly growing.

In In the textile industry, polyester has certain decisive advantages, including a high strength, a soft touch, a stretch resistance, Stain resistance, Machine washability, crease resistance and abrasion resistance. However, polyester is not optimal in terms of its hydrophobicity, Pilling, Statics, dyeability, inactive surface as a medium for arrest, d. H. the softening or the wettability improving compounds, and lack of breathability. About that In addition, in the 1960s and 1970s, polyester textiles from the Consumers barely noticed and were synonymous with the phrase "made cheap" and were due to mocking the horrible colors associated with which polyester has been. This latter problem is largely due to unavailability a big one Attributed to selection of dyes that are compatible with polyester. To counter this perception, The industry made strong efforts to set the characteristics of polyester.

one the problem areas that the industry was trying to improve includes the characteristic feature that polyester over the Uptake of polar or charged compositions, d. H. towards fabric softeners, Finishes and dyes, is very stable. In the past It has been taught that many synthetic fibers, such as those of cellulose acetate, Cellulose triacetate, acrylonitrile, polyesters, polyamides and polymers Hydrocarbon polymers, neither with base dyes nor with Cotton dyes are sufficiently dyed. Current procedures to dye close of polyester exchanging chemical substitution of terephthalate by compounds such as isophthalate and sulfoisophthalate, which inhibit uptake of the Dye, thereby improving the chemical penetration of the dyes by applying a high temperature, emulsified aromatic and / or chlorinated aromatic solvents, adding dye to the molten polyester and the use of crosslinking polymers for bonding the pigment with the textile fabric is improved. U.S. Patent No. 3,381,058 discloses a method of manufacture a poly (1,4-cyclohexylenedimethylene terephthalate) fiber having dispersed therein, non-fiber-forming polyester for the purpose of improving dyeability. Similar Targets are achieved by methods disclosed in US Pat. 3,057,827 (preparation of a high molecular weight linear condensation copolyester from linear polyester-forming compounds with an essential one Component of a sulfinite residue) and U.S. Patent No. 3,018,272 (Preparation of compounds comprising a polyester under Use of a metallic salt of a sulfonate) described are.

One Another problem with polyester relates to the difficulty of removing oily and / or hydrophobic stains. These stains often adhere firmly to the textile fabric or the fiber and lead to a permanent patch.

Consequently are methods for improving the surface characteristics of polyester been developed in an effort to improve dyeing, stain resistance, and other properties associated with the highly hydrophobic nature of Polyester are associated to improve. For example, chemical Procedures, such as nucleophilic substitution by nucleophilic Attack on ester carbonyl or hydrolysis; Surface polymerization by crosslinking a topical finish with either the fiber or the textile fabric; chemical penetration of the polyester polymer with aromatic compounds; and topical application of a surface coating from a aqueous Solution, to the polyester affinity has. Nevertheless, these processes often have inherent deficiencies, such as the cost of chemicals, Energy and capital equipment, the use of for the environment dangerous solvents a limited flexibility and negative impact on the strength of the material and other aesthetic Properties of textile fabrics on.

The GB 2 296 011 A discloses enzymes naturally formed by a fungus of the species Fusarium solanii var. minus T.92.637 / 1, including a cutinase with an isoelectric point of 7.2 and a molecular weight of 22 kDa, which are useful in detergent compositions for the removal of Dirt and stains based on fatty acids are useful.

The US 5,512,203 discloses cleaning compositions comprising a cutinase enzyme and a polyesterase-compatible surfactant. The microbial cutinase is derived from Pseudomonas mendocina and is used in an improved process for the enzymatic purification of a material with a cutin or cutin-like contaminant.

The PCT Publication No. WO 97/43014 Bayer AG) describes the enzymatic degradation of Polyesteramide by treatment with an aqueous solution containing an esterase, lipase or protease.

The JP 5 344 897 A (Amano Pharmaceutical KK) describes a commercial lipase composition which is dissolved in solution with an aliphatic polyester, with the result that the fiber texture is improved without loss of strength. Polymers of aliphatic polyethylene are also disclosed which are obtained by lipase from Pseudomonas spp. can be reduced.

The PCT Publication No. 97/33001 (Genencor International, Inc.) discloses a method for the improvement the wettability and the absorbency of a polyester fabric by treatment with a lipase.

The PCT Publication No. WO 99/01604 (Novo Nordisk) describes a method for depilling or the prevention of balling a polyester fiber or a textile fabric and for color clarification such Textile tissue by reacting with an enzyme hydrolytic activity either ethylene glycol dibenzyl ester (BEB) and / or terephthalic acid diethyl ester (ETE) owns.

The PCT Publication No. WO 00/34450 (Novo Nordisk A / S) describes certain variants of fungal cutinases of Humicola insolens of Fusarium solani pisi with an improved thermostability. The use of such cutinases in the improvement of the functional finish or finish of a PET-containing Yarn or textile fabric by treatment with the cutinase variant is described.

The PCT Publication No. WO 97/27237 (Novo Nordisk A / S) describes a process for the enzymatic Hydrolysis of cyclic oligomers of poly (ethylene terephthalate). The described hydrolytic process takes place in a textile finishing step, which involves the treatment of the yarn after it is dyed and was entangled into a fabric. A cutinase can act as a biopolyester hydrolyzing enzyme can be used.

It Although progress has been made in the area of improving the quality of polyester but there is still a need in the industry additional Process for the preparation of polyesters with improved characteristics.

SUMMARY THE INVENTION

It is an object of the present invention to provide a method of modifying surface properties to provide a polyester fiber or article to enable an improved subsequent modification thereof.

It Another object of the invention is a method for modifying the surface properties of a To provide polyester fiber or an object, so that the Fiber or article has improved characteristics with respect to having the uptake of cationic compounds.

It is still another object of the invention, a polyester fiber or an object with an improved ability to receive a To provide dye.

It is yet another object of the invention, a process for the preparation a polyester fiber with improved performance characteristics, such as dyeability, chemical modification and / or textile finishing.

It is yet another object of the invention, a method for enzymatic To provide a polyester in which the polyester subsequently with organic acids is treated to further the hydrophilicity and / or surface charge to increase and thereby the uptake of cationic compounds and / or the stain resistance of the textile fabric.

It is yet another object of the invention to provide a process for the enzymatic treatment of a polyester,
in which the polyester is more capable of reacting and forming bonds with chemicals that react and form bonds with alcohols and carboxylic acids.

According to the present The invention will provide a method for modifying the surface of a Polyester article, which comprises treating the polyester article with an enzyme with polyesterase activity for a time and under conditions so that the chemical properties of the surface are modified be a surface-modified Polyester produce. Preferably, the resulting surface-modified Polyester article subjected to further treatment, wherein the benefit of treatment by enzymatic surface modification was improved. In a preferred embodiment, the enzymatic surface-modified Polyester article reacted with a chemical reagent to a non-covalent interaction between the surface of the Polyester and the reagent to produce. In a further preferred embodiment becomes the enzymatically surface-modified Polyester reacted with a chemical reagent to give a covalent bond between the polyester and the reagent or a to create another connection. In this embodiment, it is possible to have a to form such bond enzymatically.

A preferred covalent interaction between the chemical reagent and the surface modified Polyester of the invention comprises treating the polyester with a chemical, leading to a further increase in hydrophilic Groups on the surface the composition leads. Another preferred covalent interaction includes the others chemical or enzymatic derivatization of the surface of a Polyester with a reagent carrying a desired functionality, for example Paint or dye, antimicrobial, antiperspirant, deodorising, Stain-preventing or textile finishing activity. A Particularly preferred covalent interaction involves treatment of the surface modified Polyester article with a dye to form a covalent Dye-polyester bond.

A preferred non-covalent interaction between the chemical Reagent and the surface-modified Polyester of the invention comprises treating the polyester with a dye which forms a non-covalent bond with the polyester forms. Other preferred non-covalent interactions include treating the surface of the surface modified Polyester with a reagent which carries a desired functionality, for Example color or dye, stain-preventing, antimicrobial, Antiperspirant, deodorant or textile finishing activity.

In a process embodiment of the invention, there is provided a process for improving the incorporation of a cationic compound onto a polyester article starting material comprising the steps of obtaining a polyesterase enzyme; Contacting the polyesterase enzyme with the polyester article starting material under conditions and for a time suitable for providing surface modification of the polyester article starting material by the polyesterase and producing a surface modified polyester; and contacting the modified polyester Following or at the same time as the enzymatic treatment step with a cationic compound, the adhesion of the cationic compound to the modified polyester is improved as compared with the polyester starting material. Preferably, the polyesterase is contacted with the polyester article in conjunction with a surfactant.

In a method embodiment The invention relates to a polyester article according to the method of the invention produced. Preferably, the polyester article has an improved Dye uptake, antimicrobial activity, stain resistance, Antiperspirant effect, deodorizing effect, conditioning effect, Hydrophilicity, wettability and / or the ability to absorb others cationic compounds in comparison with the same polyester, with the exception that this is not treated enzymatically. In one of the strongest preferred embodiment For example, the polyester article is dyed with a cationic dye.

SHORT DESCRIPTION THE DRAWINGS

The 1 discusses the effect of polyesterase treatments on the dyeability of Dacron 54.

The 2 discusses the effect of polyesterase treatments on the dyeability of Dacron 64.

DETAILED DESCRIPTION OF THE INVENTION

According to the present The invention will provide a method for modifying the surface of a Polyester article, which comprises treating the polyester article with a polyesterase enzyme for includes a time and under conditions, so that the chemical properties the surface be modified to produce a surface-modified polyester. Preferably, the resulting surface-modified polyester article becomes undergo further treatment, taking advantage of the treatment by the enzymatic surface modification was improved. In a preferred embodiment, the enzymatic surface-modified Polyester article reacted with a chemical reagent to a non-covalent interaction between the surface of the Polyester and the reagent to produce. In a further preferred embodiment becomes the enzymatically surface-modified Polyester reacted with a chemical reagent to form a covalent Bond between the polyester and the reagent or another Create connection.

A preferred covalent interaction between the chemical reagent and the surface modified Polyester of the invention comprises treating the polyester with a chemical, leading to a further increase in hydrophilic Groups on the surface the composition leads. Another preferred covalent interaction includes the others chemical or enzymatic derivatization of the surface of a Polyester with a reagent carrying a desired functionality, for example Paint or dye, antimicrobial, antiperspirant, deodorising, Stain-preventing or textile finishing activity. A Particularly preferred covalent interaction involves treatment of the surface modified Polyester article with a dye to form a covalent dye-polyester bond to build.

A preferred non-covalent interaction between the chemical Reagent and the surface-modified Polyester of the invention comprises treating the polyester with a dye which forms a non-covalent bond with the polyester forms. Other preferred non-covalent interactions include treating the surface of the surface modified Polyester with a reagent which carries a desired functionality, for Example color or dye, stain-preventing, antimicrobial, Antiperspirant, deodorant, or textile finishing activity.

In a method embodiment The invention relates to a method for improving the reception of a cationic compound on a polyester article starting material comprising the steps of obtaining a polyesterase enzyme; contacting the polyesterase enzyme with the polyester article starting material under conditions and for a time for the providence of a surface modification of the polyester article starting material through the polyesterase and the preparation of a surface modified Polyesters are suitable; and contacting the modified one Polyester article in connection or simultaneously with the enzymatic Treatment step comprising a cationic compound, thereby the adhesion of the cationic compound to the modified polyester is improved in comparison with the polyester starting material. Preferably, the polyesterase is incorporated with the polyester article Contacted with a surfactant.

In a method embodiment The invention relates to a polyester article according to the method of the invention produced. Preferably, the polyester article has an improved Dye uptake, antimicrobial activity, stain resistance, antiperspirant effect, deodorizing effect, finishing effect, Hydrophilicity, wettability and / or the ability to form other cationic compounds compared to the same polyester, except that this is not treated enzymatically. In a most preferred embodiment For example, the polyester article is dyed with a cationic dye.

"Polyester" as used herein means a linear polymeric molecule arranged in a chain Contains ester groups and from the condensation of a diacid with a diol or out the polymerization of hydroxy acids be derived. The present invention can be applied to both aliphatic as well as to use aromatic polyesters. However, they are special prefers objects made of aromatic polyester, used to make fiber and resin which are a synthetically produced long-chain Polymer comprising at least 85 wt .-%, preferably at least 90% by weight, and most preferably at least 95% by weight of an ester a substituted aromatic carboxylic acid, such as substituted terephthalic acid or of para-substituted hydroxybenzoate. Other useful Polyester articles shut down those consisting of block polymer, yarns, textile fabrics, films, Resins and powders are made. The main polyesters in industrial Close insert Polyethylene terephthalate (PET), tetramethylene terephthalate (PTMT), Polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT) and polyethylene naphthalate (PEN), polycyclohexanedimethylene terephthalate (CHDMT), polyethylene-4-oxybenzoate) A-Tell, polyglycolide, PHBA and 2GN on. Polyester, as used herein, may be in the form of a fiber, a yarn, a textile fabric, a textile article or any have other composition, in which polyester fibers, yarns or textile fabrics are used.

"Polyesterase" means an enzyme that a significant ability to catalyze the hydrolysis and / or surface modification of PET. In particular, the notifying parties found that enzymes with a hydrolytic activity across from PET under the conditions given in the UV and MB assays, the in Examples 1 (a) and 1 (b) (herein referred to as the "UV assay" and the "MB assay", respectively) the treatment of polyester resins, films, fibers, yarns and textile fabrics useful for modifying their properties. As a result, the in Example 1 (a) and 1 (b) provided for the isolation of Polyesterase enzymes and / or for determining the polyesterase activity of a Enzymes are used.

The Applicants have surprisingly determined that enzymes according to the present Invention represent a subclass of enzymes that have a significant activity across from Possessing polyester and for providing improved surface modification effects are capable. In contrast, enzymes defined by assays in the art appear more general to be and a larger occurrence to show false positive results. Assays for measurement the hydrolysis of mono- and diester units are designed as the ETE and BEB hydrolysis measuring assays described in WO 99/01604 are described in identifying a large number of enzymes useful, some of them happen to be a useful one Polyesterase activity can have. However, these assays are based on the hydrolysis of mono- and Diestermolekülen. Consequently, these results often do not allow predicting the likelihood of a specific enzyme is the surface of long-chain polyesters successfully modified. Example 1 (d) shows that assays that for one Designed small-molecule hydrolysis are generally enzymes that bind against the mono- and Diestermoleküle useful are while they do not predict with accuracy whether such enzymes are an activity against Fibers from big ones Repeating polymers, such as long-chain polyesters.

Consequently For example, the polyesterase enzymes of the present invention provide a positive Result according to one or both of the polyesterase assays described herein. The activity of the enzymes of the invention in solution an absorption of at least 10% over the control dummy, preferably 50%, and most preferably 100% or more than that Control blank. In a most preferred embodiment The polyesterase enzymes of the invention give a positive result in both assays, which is at least twice the increase in Absorption measurement of the blank is.

suitable Polyesterases can from animal, plant, fungal and bacterial sources be isolated. In terms of The use of polyesterases derived from plants, polyesterases in the Pollen numerous plants are present.

Polyesterases may also be derived from a fungus, such as Absidia spp .; Acremonium spp .; Aga ricus spp .; Anaeromyces spp .; Aspergillus spp., Including A. auculeatus, A. awamori, A. flavus, A. foetidus, A. fumaricus, A. fumigatus, A. nidulans, A. niger, A. oryzae, A. terreus and A. versicolor; Aeurobasidium spp .; Cephalosporum spp .; Chaetomium spp .; Cladosporium spp .; Coprinus spp .; Dactyllum spp .; Fusarium spp., Including F. conglomerans, F. decemcellulare, F. javanicum, F. lini, F. oxysporum, F. roseum and F. solani; Gliocladium spp .; Helminthosporum spp., Including sativum; Humicola spp., Including H. insolens and H. lanuginosa; Mucor spp .; Neurospora spp., Including N. crassa and N. sitophila; Neocallimastix spp .; Orpinomyces spp .; Penicillium spp .; Phanerochaete spp .; Phlebia spp .; Piromyces spp .; Pseudomonas spp .; Rhizopus spp .; Schizophyllum spp .; Trametes spp .; Trichoderma spp., Including T. reesei, T. reesei (longibrachiatum) and T. viride; and Ulocladium spp., including U. consortiale; Zygorhynchus spp. Likewise, it is considered that a polyesterase is found in bacteria such as Bacillus spp .; Cellulomonas spp .; Clostridium spp .; Myceliophthora spp .; Pseudomonas spp., Including P. mendocina and P. putida; Thermomonospora spp .; Thermomyces spp., Including T. lanuginosa; Streptomyces spp., Including S. olivochromogenes and S. scabies; and fiber degrading ruminant bacteria such as Fibrobacter succinogenes; and in yeast, including Candida spp., including C. antarctica, C. rugosa, torresii; C. parapsilosis; C. sake; C. zeylanoides; Pichia minuta; Rhodotorula glutinis; R. mucilaginosa; and Sporobolomyces holsaticus, can be found.

"Textile" means anything Textile fabric or yarn or product which is a textile fabric or Yarn included. examples for Fabrics that may be treated with the present invention include garments, footwear, Upholstery, curtains or hangings, Carpets, clothing for outside, strands and Products based on strand. As in the present invention used, closes Textile nonwoven textile fabric, which, for example, in the medical Industry are used.

In an embodiment be chemical compounds with the surface of the enzymatically treated Polyester be reacted. In a preferred embodiment the chemical compounds are chosen to be a covalent Bond with the surface-modified Polyester form and further the presence of hydrophilic groups on the surface of the polyester. The surface modification Produced with polyesterase, one assumes, an overabundance of new, exposed alcohol and carboxylate groups. According to the present Invention, these groups are then for a chemical or enzymatic Derivatization with chemicals susceptible to another increase capable of hydrophilicity and / or surface charge. Such compositions close organic acids, such as acetate, carboxylate and succinate, a. Alternatively has the derivatized polyesters have an improved ability to react with chemicals, those with carboxylic acids and / or alcohols, thereby providing the opportunity to additional To produce effects in the polyester. Acid anhydrides are one such Group of chemicals.

"Recording" means in relation to the Accommodated on a polyester article as provided herein Process of covalent or non-covalent bonding of a compound to the surface-modified polyester article, to achieve a specific effect, for. B. softening, discoloring, antistatic, Prevention of staining, antimicrobial effect, antiperspirant effect, deodorizing effect, or a different modification of the Properties of polyester fiber or textile fabric. As provided herein, provide the surface modified Polyester of the invention a superior Substrate from which additional benefits are added. Consequently, allow the surface modified Polyester compounds of the invention, for example, an improved Dye binding to polyester over a similar polyester, which differs only in that it does not treat enzymatically has been. As used herein, covalent bonding means that a molecular bond between the uptake composition and the Fiber, yarn or textile fabric is formed. In contrast means non-covalent bond that the male composition with the fiber, yarn or textile fabric through mechanisms such as hydrogen bonding, Van der Waals binding or other molecular interactions which not the formation of a molecular bond affecting the uptake composition and the fiber that joins yarn or textile includes, arrested becomes.

• • Antimikrobielle Verbindungen, wie kationische antimikrobielle Peptide und quaternäre Ammoniumsalze;
• • Tenside mit einer kationischen Natur;
• • Duftstoffe;
• • Textilweichmacher;
• • Farbstoffe und Pigmente, wie die kationischen Basisfarbstoffe, die in "Analytical Methods for a Textile Laboratory" (Analyseverfahren für ein Textillabor), 3. Auflage, Hrsg. J. W. Weaver, aufgelistet sind;
• • Textilappretur;
• • Benetzungsmittel;
• • Biofunktionelle Moleküle, die eine medizinische Wirkung bei medizinischen Polyester-Implantaten oder Vorrichtungen besitzen.

In a particularly preferred embodiment, the compound covalently or non-covalently bound to the surface comprises a "cationic compound". As used herein, cationic compound means any compound that has a cationic character and that adds a desirable property when attached to a polyester. Suitable cationic compounds for use with the present invention include:

• Antimicrobial compounds, such as cationic antimicrobial peptides and quaternary ammonium salts;
• Surfactants of a cationic nature;
• • fragrances;
• • fabric softener;
• Dyes and pigments, such as the cationic base dyes listed in "Analytical Methods for a Textile Laboratory", 3rd Edition, ed. JW Weaver;
• • textile finish;
• Wetting agent;
• Biofunctional molecules that have a medicinal effect on medical polyester implants or devices.

"Textile finish compounds" or "textile finishes" means compounds, which the textile properties of a polyester fabric or yarn improve. Examples are compounds which are the softness, flame retardancy, Wrinkle resistance, the absorption level, the stain resistance, Resistance to microorganisms or insects, persistence across from UV light, heat and impurities, running-in resistance, abrasion and wear resistance, resistance across from Pilling, the fall ability, the insulating properties, wrinkle resistance and / or the static resistance of polyester fabrics (see, e.g., Textile Processing and Properties, Tyrone Vigo, Elsevier Science B.V. (1994)).

"Treatment" means regarding the Treatment with polyesterase the method of applying the polyesterase onto a polyester article, allowing the enzyme to react with the surface of the polyester article is capable of exhibiting its hydrophilicity such a measure to increase, that the attachment of cationic compounds in significant Way is improved. Generally this means that the polyesterase mixed with the polyester article in an aqueous environment which facilitates the enzymatic action of the polyesterase.

The Treat according to the present The invention involves preparing an aqueous solution that is an effective amount a polyesterase or a combination of polyesterases together Contains other optional ingredients, including, for example a buffer or a surfactant. An effective amount of a polyesterase enzyme composition is a concentration of polyesterase enzyme necessary for the desired Purpose is sufficient. Thus, for example, an "effective amount" of polyesterase in a composition intended for the improvement of dye uptake according to the present invention The amount that is meant for the desired Effect ensures, for. For example, the appearance of the colored article in comparison with a similar one Process which does not use polyesterase to improve. Likewise, an "effective Amount "of polyesterase in a composition intended for the improvement of the softness of a polyester fabric is intended the amount, in combination with a fabric softening compound measurable improvements in softness compared to a similar one Method without the polyesterase provides. The amount of used Polyesterase hangs also from the equipment used, the applied process parameters, eg. B. the temperature of the polyesterase treatment solution, the Exposure time to the polyesterase solution and the polyesterase activity from (z. B. requires a specific solution a lower concentration of polyesterase, where a more active Polyesterase composition is used in comparison with a less active polyesterase composition). The exact concentration of polyesterase in the aqueous Treatment solution which the fabric to be treated is added, can be easily by a Professional based on the factors mentioned above as well as the desired Determine the result. However, the inventors herein found that the advantage disclosed herein is a relatively rigorous Requires polyesterase treatment. Thus, those described herein Benefits probably not with moderate levels of polyesterase and relatively short (less than 1 hour) treatment times. Nevertheless, it is possible that a laboratory-produced polyesterase or a polyesterase with an exceptionally high activity could be obtained on polyester The less than 1 hour of treatment would need to get the desired one utility grade and thus within the scope of the present invention would fall. Likewise, the use of large amounts of polyesterase over short periods also lead to the achievement of the advantages described herein.

In a preferred treatment embodiment, a buffer is employed in the treatment composition such that the concentration of buffer is sufficient to maintain the pH of the solution within the range in which the employed polyesterase exhibits the desired activity. The pH at which the polyesterase exhibits activity depends on the nature of the polyesterase used. The exact concentration of the buffer used depends on several factors which the skilled person can easily take into account. For example, in a preferred embodiment, the buffer and buffer concentration are selected to maintain the pH of the final polyesterase solution within the pH range required for optimal polyesterase activity. The determination of the optimum pH range of the polyesterase of the invention can be determined according to well-known techniques. Suitable Puf Also, those having a pH within the range of activity of the polyesterase are well known to those skilled in the art.

In addition to Polyesterase and a buffer contains the treatment composition preferably a surfactant. Suitable surfactants include any Compatible with the polyesterase and the textile fabric used Surfactant, including, for example, anionic, nonionic and ampholytic surfactants. Suitable anionic surfactants include but are not limited linear or branched alkylbenzenesulfonates; Alkyl or alkenyl ether sulfates with linear or branched alkyl groups or alkenyl groups; Alkyl or alkenyl sulfates; olefin; Alkanesulfonates and like. Suitable counterions for anionic surfactants include but are not limited on, alkali metal ions, such as sodium and potassium; alkaline earth metal ions, such as calcium and magnesium; Ammonium ions; and alkanolamines with 1 to 3 alkanol groups with a carbon number of 2 or 3. Ampholytic Close surfactants z. B. quaternary Ammonium salt sulfonates and betaine type ampholytic surfactants. Such ampholytic Surfactants possess both the positively and negatively charged groups in the same molecule. Nonionic surfactants generally include polyoxyalkylene ethers as well higher fatty acid or alkylene oxide adduct thereof and fatty acid glycerol monoester. mixtures of surfactants can also used in the manner known to those skilled in the art become.

In a particularly preferred embodiment of the invention, it is desirable to add glycerol, ethylene glycol or polypropylene glycol to the treatment composition. Applicants have found that the addition of glycerol, ethylene glycol or polypropylene glycol contributes to increased polyesterase activity on polyester. Applicants have determined that defoaming and / or lubricants such as Mazu ^®, have a desirable effect on the activity of Polyesterase.

In some embodiments it may be desired be explained above To adjust parameters for the purpose of regulating enzymatic degradation. For example, the pH can be adjusted at certain times be to the activity to delete the polyesterase and unwanted excessive degradation to prevent. Alternatively you can Other art-recognized methods of erasing enzyme activity have been used be, for. B. a protease treatment and / or heat treatment.

As As can be seen above, the present invention is in the Production of laundry detergents useful. For example, it may be desired the inclusion of a cationic laundry additive, d. H. a fabric softener or other such compounds, which the feeling Improve the look or comfort of washed textiles, to support. In this case, the present invention provides methods around the polyester during to modify the washing cycle, so as to accommodate the beneficial Aid to assist.

EXAMPLES

example 1

This Example provides two assays demonstrating polyesterase activity in a identify potential enzyme candidates. Preferably shows the enzyme polyester hydrolysis activity in both Assays.

(A) Assay for the enzymatic Hydrolysis of long-chain polyester polymer fibers on the basis of UV light absorbance (UV assay)

This Assay tracks the release of terephthalate and its esters, which result from the enzymatic hydrolysis of polyester, and measures the hydrolysis product by subjecting the sample to the UV spectrum and the absorption is measured.

Materials:

Enzyme Reaction Buffer: 100 mM Tris, pH 8, optionally containing 0.1% Brij®- ³⁵

Procedure:

• 1. The polyester is washed with hot water and air dried. Applicants recommend and herein, the use, as an example of such easily obtained standardized polyesters how woven Dacron ^® 54 polyester (from Testfabrics) (used in the following description). However it is often preferred to use the specific polyester substrate for which a modification is desired, e.g. Textile fabric, powder, resin or foil, thereby ensuring that the chosen enzyme has optimal activity on that specific substrate. In such a case, it is only necessary to replace the Dacron described below with the desired polyester substrate.
• 2. 16 mm (5/8 inch) circular swatches are cut out of the ^Dacron® 54.
• 3. The swatches are sealed in a reaction buffer 12-well microtiter plates under orbital shaking Incubated at 250 rpm. A typical reaction batch has 1 ml as Volume, with 10 μg Enzyme. Three samples should be tested: (1) Substrate + Buffer, (2) enzyme + buffer, (3) enzyme + substrate + buffer.
• 4. The reaction is allowed to proceed for 18 hours at 40 ° C.
• 5. Terephthalate and its esters have characteristic strong absorbance peaks around 240-244 nm - to _(M ε 10,000). Therefore, when these species are released into the liquid phase of the reaction by enzymatic hydrolysis, the absorption of the liquid phase of the reaction mixture at these wavelengths is increased.
• 6. To determine if hydrolysis has occurred determine the absorption of the liquid phase the enzyme + substrate + buffer reaction at about 240-250 nm. The appropriate blanks (substrate + buffer and enzyme + buffer) have to be subtracted. These measurements can be done in a quartz cuvette a spectrophotometer or a UV-transparent microtiter plate in a microplate reader, that for the required wavelengths capable is carried out become.
• 7. To prove that the absorption measurements are higher than at the blanks, actually up Terephthalate compounds are due, should have an absorption spectrum of the reaction mixture of 220-300 nm be scanned. Only a peak around 240-244 nm should be considered actual Reaction product can be considered.
• 8. Terephthalic acid and diethyl terephthalate are commercially available. Your absorption spectra should serve as standards.

(B) Assay for the enzymatic Hydrolysis of long-chain polyester polymer fibers based on the binding of methylene blue (MB assay)

This Assay utilizes the binding of methylene blue, a cationic dye, to the free carboxylate groups by hydrolysis of polyester be generated.

materials

Enzyme reaction buffer: 100 mM Tris, pH 8, containing 0.1% ^Triton® X-100
Wash buffer: 100 mM, MES pH 6.0
Dye solution: 0.1 mg / ml methylene blue in 1 mM MES, pH 6.0
Dye Elution Buffer: 0.5 M NaCl in 10 mM MES, pH 6.0
Woven Dacron 54 polyester from Testfabrics.

Procedure:

• 1. The polyester is washed with hot water and air dried. Applicants recommend the use of such easily obtained standardized polyesters how woven Dacron ^® 54 polyester (from Testfabrics) (used in the following description). However, it is often preferred to use the specific polyester substrate for which modification is desired, e.g. Textile fabric, powder, resin or foil, thereby ensuring that the chosen enzyme has optimal activity on that specific substrate.
• 2. 16 mm (5/8 inch) circular swatches are cut out of the ^Dacron® 54.
• 3. The swatches are sealed in a reaction buffer 12-well microtiter plates under orbital shaking Incubated at 250 rpm. A typical reaction batch has 1 ml as Volume, with 10 μg Enzyme. Blank samples (samples without enzyme) should also be tested be subjected.
• 4. The reaction is allowed to proceed for 18 hours at 40 ° C.
• 5. The reaction solution is removed by suction and the swatches are then washed with: (1) 1 ml of incubation buffer to remove residual enzyme; (2) 1 ml of water to remove the incubation buffer; (3) 1 ml of 100 mM MES buffer to equilibrate the swatches to a pH of 6; and (4) again 1 ml of water to free the MES buffer.
• 6. 1 ml of dye solution is added to each well and the plate is shaken at 250 rpm for 20 minutes at 40 ° C. In this case, methylene blue is used. However, other cationic dyes or "reporter" reagents may also be used. The hydrolysis by 100 mM NaOH can be used as a positive control.
• 7. The excess dye (Methylene blue) is removed by suction, and the wells are washed 3 times with 1 ml of water.
• 8. 1 ml of Dye Elution Buffer is added to each well, and the plate is shaken at 250 rpm at 40 ° C for 30 minutes.
• 9. 300 μl of the dye eluate become a plate from each well transmitted with 96 wells, and the absorption peak at 650 nm is determined.

In Each of the above assays described in Examples 1 (a) and 1 (b), the absorption measurement should be a significant one show hydrolytic product which is not experimental or non-hydrolytic Attributable to effects. One skilled in the art These effects are known and how to interpret them before these protects from results.

(C) Assay for the enzymatic Hydrolysis of diethyl terephthalate (DET)

This spectrophotometric assay tracks the change in the UV spectrum of DET, which accompanies its hydrolysis.

DET has a characteristic absorption peak around 244 nm ( _M ε _M ~ 10,000). The ester hydrolysis products have a lower absorbance and the peak is shifted to 240 nm. Thus, the hydrolysis of DET can be monitored by measuring the decrease in absorbance at 250 nm.

reagents:

Enzyme reaction buffer: 10 mM Tris, pH 8
DET stock solution: 100 mM in DMSO

Procedure:

• 1. Dilute DET 1000-fold in reaction buffer to a 100 μM solution too receive.
• 2. Set the spectrophotometer wavelength to 250 nm.
• 3. Add enzyme and change monitor the absorption or the Absorptionsmaßes. In a separate Sample of the same volume of buffer without enzyme the change of the absorption resulting from background hydrolysis.
• 4. The reaction rate is calculated from the linear part of the Reaction Progress Curve calculated and reported as -mAU / min, and the Reaction rate of the buffer blank is subtracted.

D. Comparison of the results PET and DET assays

• ¹ (Kommerzielles Produkt, erhalten von Novo Nordisk)
• ² (Kommerzielles Produkt, erhalten von Genencor International, Inc.)

• ³ (Schweineleber-Esterase I und II, erhalten von Boehringer Mannheim ChiraZyme^TM Lipases & Esterases Screening Set (Deutschland))
• ⁴ (Alle aufgelisteten E-Serien-Esterasen wurden vom ThermoCat^TM R&D-Produktsortiment von Thermogen (Chicago, IL) erhalten.)
• ⁵ (Alle "ESL"-Serien-Esterasen wurden aus der Diversa Esterase/Lipase Clone Zyme^TM Bibliothek erhalten.)

• ⁶ (Alle ChiroCLEC^TM-Enzyme wurden aus dem Altus Corp ChiroScreen^TM Enzyme Set (Cambridge, Massachusetts) erhalten.)

Enzymes with esterase and / or lipase activity were obtained from numerous sources and assayed according to the assays described in Examples 1 (a), 1 (b) and 1 (c). The relative results are tabulated in Table I, taking into account the absorbance of the hydrolysis product of P. mendocina cutinase at 1.0. Table I

• ¹ (commercial product, obtained from Novo Nordisk)
• ² (Commercial product, obtained from Genencor International, Inc.)

• ³ (Porcine liver esterase I and II, obtained from Boehringer Mannheim ChiraZyme ^™ Lipases & Esterases Screening Set (Germany))
• ⁴ (All listed E series esterases were obtained from the ThermoCat ^™ R & D product range from Thermogen (Chicago, IL).)
• ⁵ (All "ESL" series esterases were obtained from the Diversa Esterase / Lipase Clone Zyme ^™ library.)

• ⁶ (All ChiroCLEC ^™ enzymes were obtained from the Altus Corp. ChiroScreen ^™ Enzyme Set (Cambridge, Massachusetts).)

As From the above data, almost all of the tested enzymes an activity in the DET assay for (diesterase activity). However, only owns one of the enzymes tested showed significant activity in both PET assays. In view of this, it is obvious that it is while it's an overlap or to a crossover regarding comes from enzymes, which activity in the DET assay and also PET hydrolytic activity own a big one There are number of enzymes that are DET hydrolytic activity possess but have no polyesterase activity. As in the examples 2 and 3, the enzyme with PET activity provides a significant enzymatic Conversion of polyester fibers before. Based on these data Applicants state that the identity of an enzyme with polyesterase activity is not From this it can be predicted whether the enzyme has mono- or diesterase activity.

Example 2

enzymatic surface modification of polyester fibers with polyesterase for modifying the functional surface properties of the polyester

• • Equipment: Launder-ometer
• Treatment pH: pH 8.6 (50 mM Tris buffer)
• • Treatment temperature: 40 ° C
• • treatment time: 24 hours
• • enzyme: Cutinase of Pseudomonas mendocina at 40 ppm
• • control: Inactivated cutinase (Pseudomonas mendocina) at 40 ppm
• • Substrates: 100% polyester
• - Dacron ^® 54 (version number 777 from Test Fabrics)
• - Dacron ^® 64 (version number 763 from Test Fabrics)

Around ensure that all effects identified are solely Modification of the polyester surface were due and not on the effects of adherent protein, were the Substance samples treated with protease. After the polyesterase treatments were Cut out 16 mm (5/8 inch) slices from the treated swatches. Thereafter, the discs were treated with 5 ppm subtilisin and 0.1% nonionic Surfactant (Triton X-100) incubated to polyester-bound proteins to remove. The proportions of bound proteins were using examined by Coomassie blue staining, to ensure that minimal protein is bound to the textile fabric remained.

• • Flüssigkeitsverhältnis: 40 zu 1
• • Farbstoffkonzentration: 0,4% owf
• • Temperatur: 40°C
• • pH-Wert: 6 (1 mM MES-Puffer bei pH 6,0)
• • Zeit: 20 Minuten
• • Bewegung des Schüttlers: 200 U/min

After enzyme treatment, followed by protease / surfactant treatments, the discs were stained in a 12-well microtiter plate under the following conditions:

• • Liquid ratio: 40 to 1
• • Dye concentration: 0.4% owf
• • Temperature: 40 ° C
• PH: 6 (1 mM MES buffer at pH 6.0)
• • Time: 20 minutes
• • Movement of the shaker: 200 rpm

ΔL

= Differenz der CIE L*-Werte vor und nach dem Färben

Δa

= Differenz der CIE a*-Werte vor und nach dem Färben

Δb

= Differenz der CIE b*-Werte vor und nach dem Färben

The disks were rinsed 3 times with DI water after dyeing, air dried, and then their CIE L * a * b * values were measured using a reflectometer. The total color difference was calculated using the following formula: Delta E = square root (ΔL * 2 + Δa * 2 + Δb * 2 )

.DELTA.L

= Difference in CIE L * values before and after staining

.DELTA.a

= Difference in CIE a * values before and after staining

.DELTA.b

= Difference in CIE b * values before and after staining

(These expressions are for example at Duff & Sinclair, "Giles's Laboratory Course in Dyeing "(Giles' lab course in dyeing), 4. Edition, Society of Dyers and Colourists).

Table 1. Total color difference after dyeing with different base dyes

The results are graphical in the 1 and 2 compiled. As can be seen, polyesterase significantly affects the ability of polyester fabrics to pick up and adhere a series of cationic dyes.

Claims (14)

Method for modifying the surface of a Polyester article, comprising the following steps: (a) treating of the polyester article with a cutinase of Pseudomonas mendocina with hydrolytic activity on polyester, as by either the UV assay or the MB assay for one Time and measured under conditions, so the ability for receiving compounds on the surface of the polyester article and (b) contacting the treated polyester with a connection under conditions necessary for arresting the connection are suitable with the polyester. The method of claim 1, wherein the compound is a forms covalent bond and to increase the hydrophilicity and / or Charging the surface of the polyester is. A method according to claim 2, wherein the compound for Reaction with an alcohol and / or a carboxylic acid is capable. The method of claim 3, wherein the compound is a (n) Tissue finish, dye, antistatic compound, staining preventing compound, antimicrobial compound, antiperspirant compound and / or a deodorizing compound. Method for improving the uptake of a cationic A compound on a polyester article starting material comprising the following steps: (a) obtaining a cutinase from Pseudomonas mendocina having a hydrolytic activity on polyester, such as either measured by the UV assay or the MB assay; (b) Contact the cutinase with the polyester article starting material below Conditions and for one Time for that suitable for the enzyme to be a surface modification of the polyester article starting material provides and a surface modified Polyester supplies; (c) contacting the modified polyester article following or simultaneously with step (b) with a cationic Compound, thereby adhering the cationic compound the modified polyester compared with the polyester starting material is improved. The method of claim 5, wherein the surface modified Polyester with a cationic compound simultaneously with the Step (b) is contacted. The method of claim 5, wherein the surface modified Polyester with a cationic compound following the Step (b) is contacted. The method of claim 5, wherein the cationic compound comprises a fabric finish compound, Dye, antistatic compound, stain-preventing compound, antimicrobial compound, antiperspirant compound and / or a deodorizing compound. The method of claim 5, wherein the cationic Compound comprises a dye. The method of claim 9, wherein the dye is a basic dye is. The method of claim 5, wherein the cationic Compound a fabric finish compound includes. Use of a Pseudomonas mendocina cutinase with a hydrolytic activity on polyester, as by either the UV assay or the MB assay measured, to improve the ability a polyester fabric for containing chemical compounds, such as of cationic compounds, fabric finish compounds, dyes, antistatic compounds, Stain-preventing compounds, antimicrobial compounds, Antiperspirant compounds and / or deodorizing compounds. Use of the UV or MB assay for identification the polyesterase activity at a potential enzyme candidate. Use of the UV or MB assay according to claim 13, wherein the substrate is PET.